1. Field of the Invention
The present invention relates to an integrated waste catalyst cleaning apparatus for residual hydro desulfurization (RHDS) and vacuum residue desulfurization (VRDS) processes and a method thereof, and more particularly, to an integrated waste catalyst cleaning apparatus for residual hydro desulfurization (RHDS) and vacuum residue desulfurization (VRDS) processes and a method thereof in that a desulfurization waste catalyst produced in the residual hydro desulfurization (RHDS) and vacuum residue desulfurization (VRDS) processes can be organic solvent-cleaned and organic acid-cleaned in one reactor.
2. Description of the Related Art
According to the notice on the use of clean fuels, the sulfur content contained in the heavy oil has been gradually decreasing. In addition, the use area of the low-sulfur heavy fuel oil has been gradually expanded. Since the heavy oil such as a bunker C oil has a high sulfur content, the consumption thereof is rapidly reduced, while the consumption of light oil products has increased significantly.
Most domestic refineries have introduced heavy oil cracking and desulfurization facilities so as to cope with the light oil trend of the oil supply and demand structure and the low-sulfurization trend of the oil products. The main process for upgrading of the Heavy oil includes an Atmospheric Residue Hydro DeSulfurization (AR-HDS), a Vacuum Residue Hydro DeSulfurization (VR-HDS), a Residue Fluid Catalytic Cracking (R-FCC), and a VGO hydrotreating process (VGO-HC) and the like. Here, it should remove large amounts of sulfur and heavy metals contained in the heavy oil for a smooth operation of the process.
The hydrodesulfurization catalyst used commercially herein is a Ni—Mo/Al2O3, a Co—Mo/Al2O3 and the like. At this time, the catalyst is poisoned owing to the deposition of the sulfur and the heavy metal etc. and the life thereof come to an end. Generally, the waste catalyst is replaced with a new catalyst in one cycle or two cycle each year. The waste catalyst amount is approximately 23,000 tons per year and the new catalysts rely on imports from abroad.
In the meantime, since the catalyst self-components metals (Ni, Mo, Co, W) in addition to V, Ni and Fe and the like contained in the oil are deposited on the produced waste catalyst, it contains a considerable amount of valuable metals. The part thereof is treated through a water leaching after a soda foasting, which is most widely used method, by means of the recovery enterprise. However, there are problems in that a lot of energies is consumed owing to the hot-melt (600 to 1000° C.) and the rear end is blocked owing to the discharge of dust etc. according to the wear between the waste catalysts. Also, in case of the collection according to the water leaching, the vanadium, which is the largest content in the valuable metals, is collected and then, the molybdenum and the nickel are collected to be discarded. However, there is a problem of environmental pollution during the waste landfill owing to a burden of the disposal costs and the difficulty of a complete recovery thereof. In addition, a part of the waste catalysts is roasted and then, it exports to China etc. Accordingly, the valuable metals such as the vanadium and the molybdenum and so on, which are natural resources, have gone abroad.
The domestic refinery hydro desulfurization (HDS) process is run for a long time. However, it takes an interest in only the collection of the valuable metals, while it does not care about the process of clearing the waste catalysts. Accordingly, the domestic technical standard is below the restoration level of the waste catalysts from the key technologies to the engineering technologies.
Korea Patent Publication No. 10-2013-0026431 (publication date: Mar. 3, 2013) relates to a method for recovering catalytic metals from the residue of the refined oil and is characterized in that the residue of the refined heavy oil is pyrolyzed and combusted in a high temperature of 900° C. for the production of the ash. However, where the residue is pyrolyzed in a high temperature through the above technique, since a gamma-alumina material used as the carrier of the catalyst is changed to a beta-alumina phase and a sintering phenomenon etc. is generated in the transition metal materials such as a Ni—Mo or a Co—Mo etc., there is a limit in that only the valuable metals are collected without the reusing it.
Also, Korea Patent registration No. 10-1434437 (Registration Date: Aug. 20, 2014) filed and registered by the present applicant relates to a reproduction system of the desulfurization waste catalyst in residual hydro-desulfurization (RHDS) and vacuum residue hydro-desulfurization (VRHDS) processes. In the waste catalyst recovery system implemented by the above technology, since each step processed in a cleaning tank, a drying tank, and a collecting tank is conducted in the different devices, there are problems in that the installation expenses is increased and the working is inconvenient.